Production of dicarboxylic acids



mrss PATENT 'orrics.

ARTI'IUE'G. WILLIAMS, OF GRANTWO OTD, NEW JERSEY, ASSIGNOR- TO THE BARRETT COMPANY, A CORPORATION OF NEW JERSEY; v

. PRODUCTION OF DICAR-BOXYLIG ACIDS.

No Drawing.

To aZZ whom it may concern Be it known that I, ARTHUR G. .WILLI'AMS, a citizen of the United States, residing at Grantwood, in the county of Bergen and Stat of New Jersey, have invented certain new and useful Improvements in the Production of Dicarboxylic Acids, of which the following is a specification.

t d-, or the corresponding double bonded dihydroxy group, T

OH on --C=C-, such group in either case to form a part of a carbocyclic. ring structure. These compounds are for the most part known as orthoquinones and hydroquinones, respectively, being generally either true quinones and hydroquinones or quinones and hydroquinones so-called. Examples .(not to be exhaustive) of such compounds are phenenthraquinone, acenaphthene-quinone, retenequinone, fluoranthenaquinone, chrysenequinone, picene-quinone and the corresponding double bonded dihydroxy compounds. I have discovered that in the case of the diketonic compounds, preliminary reduction, as by sodium hydrosulfite in alkaline solution,.for example, followed by oxidation in alkaline solution by means of a suitable oxidizing agent, as by sodium peroxide, hydrogen peroxide, or, where feasible, air, leads to the production of the corresponding dicarboxylic acids. I have discovered in the case of the dihydroxy compounds that their solution in aqueous alkali followed by oxidation by means of a suitable oxidizing agent, .as by sodium peroxide, hydrogen peroxide or, Where feasible, air, leads likewise to the production of the corresponding dii pecification of Letters Patent.

' naphthenequinone and Patented July 25, 1922.

Application filed. March 22, 1921. Serial No. 454,479.

carboxylic acids. Thus, from phenanthraquinone and phenanthrenehydroquinone, diphenic acidis obtained, while from ace- 7, 8-dihydroxyacenaphthylene,

no (10H naphthalic acid is produced. Suitable substituted derivatives of the parent compounds, substituents being, for example,

alkyl, halogen, hydroxyl, sulfo, may like-.

wise be employed for the production of the corresponding substituted dicarboxylic acids. t

Inasmuch as phenanthrene and acenaphthene are comparatively plentiful, the invention will be illustrated and described specifically in connection with them and their derivaties, but it is to be understood that the invention is not restricted to these particular substances.

The usual products of the direct oxidation of phena-nthrene are phenanthraquinone and, from this, diphenic acid. Inasmuch as phenanthraquinone is a higher oxidation product of phenanthrene than is phenanthrene-hydroquinone and is therefore nearer in state of oxidation to diphenic acid than is the hydroquinone, it has not been obvious that the acid may be produced much more readily from .phenanthrene-hydroquinone,

the intermediate production of which from phenanthraquinone represents in a sense. a backward step, not to be foreseen, yet found desirable, in the production of diphenic acid.

I have found, for example, thatthe action of an oxidizing agent such as sodium peroxide on an alkaline reduced solution of phenanthraquinone or on an alkaline solution of phenanthrene hydroquinone results directly in a substantially quantitative conversion to the dicarboxylic acid, here diphenic acid, and that this oxidation will take place at comparatively low temperatures; The conversion takes place almost immediately between 50 60C. and re- I e u qulrds only a short time at a temperature oi about 35C. l his unexpected result is one of the unforeseen consequences of my invention. The sensitiveness of hydroquinones to oxidation procedure a phenanthraquinone and oxidation to the corresponding quinones is well knownand it was therefore wholly une expected that certain oxidizing agents should have shown a preference for another course. ample, that alkaline potassium permanganate, the oxidant most generally used in alkaline solution, regenerates the quinone when allowed to act oniphena-nthrenehydroquinone. Further, Anschiitz and J app found (Ber. vol. 11 page2l1) that alkaline permanganate at 100 gavewith phenanthraquinone diphenylene-ketone and only traces of diphenic acid. Inasmuch, however, as their oxidation was applied to th'e quinone unreduced, it is in no wise comparable to the peroxide process. I I

Hitherto diphenic and naphthalic acids have been made by the oxidation of phenanthrone and acenaphthene, respectively, or

the corresponding quinones, by the action in acid medium of chromic acid or'of sodium or potassium dischromate. In the case of the production of diphenic acid from phenan threne, there is obtained by the usual oxidation procedure a mixture ofunchanged phenanthrene, phenanthraquinone, and diphenic acid, and if the phenanthrenc. is not pure, as is usually the case, other products including acids are produced, thus forming a mixture from which the separation of a diphenic acid of a high degree of pur' matter of considerable diliiculty. .he oxidation is carried far enough to oxid ze all of the phenanthrene. and ohenanthraquinone, much of the diphen cid is itself "either case is very low.

If diphenic acidis produced froni-pl en'anthraquinone, there is obtained by the usual v diphenie acid, and if the quinone s crude, 'otlier products includ ng'jacid's 'Wl'll .'b6 producedg thus form f'ing a mixture requiring a separation of the 1 making" even much moreditlicu'lt the productio'n ofa"diphenic acid ofa' high degree "purity. Here too, in'the 'case'ot' the use of phenanthraquinone, the yield is coinp'ara-" tive'ly small. Thus Oysterand: Adkinsjl' j i'mfch'e'm, 'Soc'.43,2Q8%l921 even by improvement on the ir'eviou'slyfdescribed procedures,"were able by'the usual chroniate L oxidation to secure a'yieldof' only of diphenici'a c'id from"phena-nthraquinone that 5 Q had'b'een purified by means of sodiur'n'bisul- 'diph'eni'c acid from other prbduc'ts, thereby In the caseof the' production 'oi tfnaphth'alic ;acid*'fr,om "acena phthe'n'e, the direct 'oxi datio'n process is a prolonged operationsub-- Experimentation shows, for ex-- ure of unchanged ject to practically the same difliculties as in the case of phenanthrene, and unless acetic acid is used as the menstruum for the reaction, thereby greatly increasing the cost of production and this still with a prolonged operation, the naphthalic acid is only difiicultly. obtainable and the yield is very small.

By my process the principal diflicultiesof other processes are not encountered and the production of the acid may be had rapidly, in high degree of purity, andwvithout the necessityiof separations from troublesome by-products. Moreover, the yield is very high, the essential reaction being in all probability quantitative. Thus, a yield of 86% and upwards may be,=-ob.tained from purified phenanthraquinone and a yield of 52% may be obtained =eve1r-fn0m--a crude phenanthraquinone which had been made by chromate oxidation from a phenanthrene of but purity. This crude phenanthraquinone had been prepared only bybeing washed with a soda solution. great improvement overall other processes for the production of diphenic acid to-have obviated the desirability of using a purified phenanthraquinone, or of a highly pure phenanthrene in-theproduction of the-former. The purification of a. crude phenanthraquiuone requires large amountsofsodium bisullite in a leeching or, digestingoperation.

I have discovered that the preliminary re-' It is a veryspecific agents, such as sodium peroxide, hy

' 10 parts of 'phenanthraquiiione ma'y'be warmed untlit dissolves 111a solution o 100 parts of 20% sodium hydroxide and QO' parts of solid sodium hydrosulfite. The 'finalJ o- Jlution maybe pouredonto ice-undue parts offsoditmi a tionQ The" resultant system may then be warmed to about 0 50" 'or-until the green 'color which it possessed has disappeared.

"filtrate acidified with hydrdchloric acid, thusca'using the diphenic acid to be precipitated; The copiously precipitated dipheiiic 'acictmay be filteredo'tf and washedmith water. Theyield has'been found to 86.2% 'oftheoretical yield.

I Naphthalic acid', for another' example, may be made in an exactly analogous? manner. In'the case of thefproduction ofzl'this be about de. rapidly and ,thoroughly" st rred into the 'coldnce-containmg solu- The solution then be'filtered and the I acid either from acenaphthenequinone 01 from 7, 8-dihydroxy acenaphthylene,=blow- 2. The process of producing a dicarboxylic acid from an aromatic compound containing a double bonded dihydroxy group,

I on on -C=C, forming part of a carbocyclic ring structure, and having an existent corresponding diketonic compound, which comprises dissolving the said dihydroxy compound in an alkaline solution, and oxidizing the solution. 3. The process of producing a dicarboxylic acid from an aromatic compound containing a diketonic group,

00 Ill forming part of a carbocyclic ring structure, which comprises dissolving the said compound in a suitable alkaline reducing solution, and oxidizing the solution by means of a peroxide.

4. The process of producing a dicarboxylic acid from an aromatic compound containing a double bonded dihydroxy group,

forming part of a carbocyclic ring structure and having an existent corresponding diketonic compound, which comprises dissolving the said dihydroxy compound inan alkaline solution, and oxidizing the solution by means of a peroxide. I

5. The process of producing a dicarboxylic acid from an aromatic compound containing a diketonic group,

forming part of a carbocyclic ring structure, which comprises dissolving the said compound in an alkaline hydrosulfite solution and oxidizing the solution by means of a peroxide.

6. The process of producing diphenic acid from phenanthraquinone which comprises dissolving the said quinone in a suitable alkaline reducing solution, and oxidizing the solution.

7. The process of producing diphenic acid from phenanthraquinone, which comprises dissolving the said quinone in an alkaline hydrosulfite solution, and oxidizing the solution.

8. The process of producing diphenic acid from phenanthraquinone, which comprises dissolving the said quinone in an alkaline reducing solution, and oxidizing the solution by means of a peroxide.

9. The process of producing diphenic acid from phenanthraquinone, which comprises dissolving the said quinone in an alkaline hydrosulfite solution, and oxidizing the solution by means of a peroxide.

10. The process of producing diphenic acid from phenanthraquinone, which COIllprises dissolving the said quinone in an alkaline hydrosulfite solution, and oxidizing the solution by means of sodium peroxide.

11. The process of producing diphenic acid from phenanthrene-hydroquinone, which comprises dissolving the said hydroquinone in an alkaline solution, and oxidiz- .ing the solution.

14. The process of producing naphthalic J acid from acenaphthene-quinone, which comprises dissolving the said quinone in an alkaline hydrosulfite solution, and oxidizing the solution. I

15. The process of producing naphthalic acid from acenaphthene-quinone, which comprises dissolving the said quinone in an alkaline reducing solution, and oxidizing the solution by means of a peroxide.

16. The process of producing naphthalic acid from acenaphthene-quinone, which comprises dissolving the said quinone in an alkaline hydrosulfite solution, and oxidizing the solution by means of a peroxide.

17. The process of producing naphthalic acid from acenaphthene-quinone, which comprises dissolving the said quinone in an alkaline hydrosulfite solution, and oxidizing the solution by means of sodium peroxide.

18. The process of producing naphthalic acid from 7, 8-dihydroxy-acenaphthylene which comprises dissolving the said 7 8- dihydroxy-acenaphthylene in an alkaline solution and oxidizing the solution.

19. The process of producing naphthalic acid from 7, 8-dihydroxy-acenaphthylene, which comprises dissolving the said 7, 8- dihydroxy-acenaphthylene in an alkaline solution. and oxidizing the solution by means ARTHUR ewmLI s, 

